Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, USA.
Chem Soc Rev. 2013 Jun 21;42(12):4991-5001. doi: 10.1039/c3cs35514d.
Propargylic esters and phosphates are easily accessible substrates, which exhibit rich and tunable reactivities in the presence of transition metal catalysts. π-Acidic metals, mostly gold and platinum salts, activate these substrates for an initial 1,2- or 1,3-acyloxy and phosphatyloxy migration process to form reactive intermediates. These intermediates are able to undergo further cascade reactions leading to a variety of diverse structures. This tutorial review systematically introduces the double migratory reactions of propargylic esters and phosphates as a novel synthetic method, in which further cascade reaction of the reactive intermediate is accompanied by a second migration of a different group, thus offering a rapid route to a wide range of functionalized products. The serendipitous observations, as well as designed approaches involving the double migratory cascade reactions, will be discussed with emphasis placed on the mechanistic aspects and the synthetic utilities of the obtained products.
炔丙基酯和膦酸酯是容易获得的底物，在过渡金属催化剂存在下表现出丰富且可调节的反应性。π-酸性金属，主要是金和铂盐，激活这些底物，使其进行初始的 1,2-或 1,3-酰氧基和膦酸酯迁移反应，形成反应性中间体。这些中间体能够进一步进行级联反应，生成各种不同的结构。本综述系统介绍了炔丙基酯和膦酸酯的双迁移反应作为一种新的合成方法，其中反应性中间体的进一步级联反应伴随着不同基团的第二次迁移，从而为广泛的功能化产物提供了快速途径。将重点讨论双迁移级联反应的偶然观察结果和设计方法，以及对获得的产物的机械方面和合成实用性的讨论。
